Confinement-Driven Photophysics in Hydrazone-Based Hierarchical Materials

Confinement-imposed photophysics was probed for novel stimuli-responsive hydrazone-based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution-like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady-state and time-resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone-based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.

Automated summary

Confinement-imposed photophysics was investigated for hydrazone-based compounds with novel stimuli-responsiveness, showing a conceptual difference in behavior between 2D and 3D porous matrices. The challenges of photoswitch isomerization in 2D scaffolds could be overcome in 3D materials by immobilizing the sterically demanding hydrazone derivatives. This approach enables the synthesis of hydrazone-based materials with fast photoisomerization kinetics in the solid state.